CN1639171A - Process for production of heteroaryl-type boron compounds with iridium catalyst - Google Patents
Process for production of heteroaryl-type boron compounds with iridium catalyst Download PDFInfo
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- CN1639171A CN1639171A CN03805187.7A CN03805187A CN1639171A CN 1639171 A CN1639171 A CN 1639171A CN 03805187 A CN03805187 A CN 03805187A CN 1639171 A CN1639171 A CN 1639171A
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 19
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 150000001639 boron compounds Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 33
- 150000002390 heteroarenes Chemical class 0.000 claims abstract description 29
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000005843 halogen group Chemical group 0.000 claims description 25
- -1 heteroaryl boron compound Chemical class 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 12
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- URYYVOIYTNXXBN-UHFFFAOYSA-N cyclooctene Chemical group [CH]1[CH]CCCCCC1 URYYVOIYTNXXBN-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical group 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical group C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 abstract 1
- 239000003446 ligand Substances 0.000 abstract 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 62
- 229910052796 boron Inorganic materials 0.000 description 34
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 33
- 229930192474 thiophene Natural products 0.000 description 31
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 description 25
- 230000002194 synthesizing effect Effects 0.000 description 19
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WGLLSSPDPJPLOR-UHFFFAOYSA-N tetramethylethylene Natural products CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000002475 indoles Chemical class 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 229910000085 borane Inorganic materials 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 150000003233 pyrroles Chemical class 0.000 description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- FKGYFHXXFBKLNH-UHFFFAOYSA-N 2-(trifluoromethyl)thiophene Chemical compound FC(F)(F)C1=CC=CS1 FKGYFHXXFBKLNH-UHFFFAOYSA-N 0.000 description 1
- OKEHURCMYKPVFW-UHFFFAOYSA-N 2-methoxythiophene Chemical compound COC1=CC=CS1 OKEHURCMYKPVFW-UHFFFAOYSA-N 0.000 description 1
- XQQBUAPQHNYYRS-UHFFFAOYSA-N 2-methylthiophene Chemical compound CC1=CC=CS1 XQQBUAPQHNYYRS-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MFSGMSKLGLUWHG-UHFFFAOYSA-N OC(C1=CC=CO1)=O.OC(C1=CC=CO1)=O.OC(C1=CC=CO1)=O.F.F.F Chemical compound OC(C1=CC=CO1)=O.OC(C1=CC=CO1)=O.OC(C1=CC=CO1)=O.F.F.F MFSGMSKLGLUWHG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001907 coumarones Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229940074386 skatole Drugs 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/46—C-H or C-C activation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/468—Iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plural Heterocyclic Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an economical, simple, and industrially advantageous process for the production of heteroaryl-type boron compounds by reacting an heteroaromatic compound with a boron compound in one step under mild conditions, which permits selective production of an aromatic heterocycle -monoboron compound and an aromatic heterocycle-diboron compound in high yield and which makes it possible to give both products at a desired ratio only by changing the charge ratio between the raw materials. Specifically, a process for production of heteroaryl-type mono- or di-boron compounds, characterized by reacting a heteroaromatic compound with bis(pinacolato)diboron or pinacolatodiborane in the presence of an iridium catalyst and a ligand such as bipyridyl.
Description
Technical field
The present invention relates to a kind of use and contain the method that iridium catalyst prepares the aromatic heterocycle boron compound.Aromatic heterocycle boron compound according to the present invention's preparation can be used as the substrate for preparing diaryl and polyaryl derivative, and this analog derivative can be used as pharmacy, agrochemistry intermediate and functional organic material and uses.
Background technology
Technology had in the past proposed the boronation method of various aromatic hydrocarbon.For example: known method has trifluoride (trifurate) lithiumation (lithionation), halogenation or the boronation method afterwards that is converted into phenyl ring, its example comprises: (1) uses method (the P.Rocca et al. of aryl halide or aryl trifluoride (trifurate) and tetramethyl ethylene ketone two boron compounds, J.Org.Chem., 58,7832,1993) (2) relate to after the aromatic ring lithiumation method (3) with the reaction of boron ester and relate to the method (A.R.Martin that reacts with the boron ester behind aryl halide and the reactive magnesium, Y.Yang, Acta..Chem.Scand., 47,221,1993).
In addition, the direct boronation example of known benzene also comprises: (4) use the halid method of boron (T.R.Kelly et al., Tetrahedron Lett., 35,7621 (1994); P.D.Hobb.et al.J.Chem.Sco.Chem.Commun., 923 (1996); T.R Hoye, M.Chen, J.Org.Chem.,, 61,7940 (1996)), (5) use method (Iverson, C.N., Smith, the M.R. that contains iridium catalyst, III.J.Am.Chem.Soc., 121,7696 (1999)), (6) use the method (Chen.H of rhenium-containing catalysts, Hartwig, J.F., Agnew.Chem.Int.Ed., 38,3391 (1999)), (7) use method (Chen, H., the Hartwig of rhodium-containing catalyst, J.F., Science, 287,1995 (2000); Cho, J.Y, Iverson, C.N., Smith, M.R., III.J.Am.Chem.Soc., 122,12868 (2000); Tse, M.K., Cho, J.Y, Smith, M.R., III.Org.Lett., 3,2831 (2001); Shimada, S., Batsanov, A.S., Howard, J.A.K, Marder, T.B., Angew.Chem.Int.Ed., 40,2168 (2001)), (8) use method (Cho, J.Y, Tse, M.K., Holmes, Science, 295,305 (2002) that contain iridium catalyst; Ishiyama, T., Takagi, J., Ishida, K., Miyaura, N., Anastasi, N.R., Hartwig, J.F., J.Am.Chem.Soc., 124,390 (2002)).
Yet the example of the boronation reaction of relevant heteroaromatic compounds does not almost have, and only known example is reacted with borine after to be that (9) are a kind of make Silver monoacetate act on indoles, the method of hydrolysis (K.Kamiyama, T.Watanabe, M.Uemura more subsequently, J.Org.Chem., 61,1375 (1996)).
Although (1) method to (9) is the example of known aforesaid aromatic nucleus boronation, there is following shortcoming in these examples in the past: lithiumation, halogenation and three that method (1) to (3) is carried out phenyl ring are fluoridized and are related to a large amount of steps, therefore produce industrial problem.And method (1) has only been utilized in employed two boron one in two boron atoms, thereby uneconomical, and method (2) and (3) have been owing to experienced the intermediate product of hyperergy, therefore to sizable restriction that causes of the functional group of employed substrate.The shortcoming of method (4) is a severe reaction conditions, and productive rate lowly reaches and form isomer when substrate contains functional group.In method (5) in the method for (7), the problem that also has catalyzer to be difficult to obtain when having the problem of requirement severe reaction conditions.In method (8), although have certain methods the boronation of phenyl ring is taken place with high yield with one step, there is not the known fragrant heterocyclic example that is applied to.In relating to the boronation method (9) that is applied to heterocycle (complex ring), has after making deleterious Silver monoacetate act on indoles the shortcoming of having to make borine to react with toxicity, explosion hazard.Consider these situations, be necessary to develop the boronation reaction of a kind of new fragrant heterocycle that can address the above problem (aromatic complex ring).
Summary of the invention
The result of the broad research of carrying out for addressing the above problem is, thereby the present inventor has studied the method that the new boronation method of heteroaromatic compounds has been established the very useful fragrant heterocycle boron compound of a kind of preparation, this method use the iridium catalyst of preparation easily and as the dipyridyl derivatives of part, this is reflected under the mild conditions effectively carry out, generate hardly by product and can make heteroaromatic compounds list boron or two boronations, the present invention is accomplished with one step.
That is, first purpose of the present invention relates to a kind of with the logical formula V or (VI) preparation method of the heteroaryl boron compound of expression,
(wherein, X, Y, Z, R
1And R
2With identical) to give a definition
It comprises: in the presence of catalyzer that contains iridium and part, make with the heteroaromatic compound of following general formula (I) expression with following general formula (III) or (IV) the boron compound reaction of expression.
(wherein, X represents that Sauerstoffatom, sulphur atom maybe can have substituent imino-, Y and Z can be identical also can be different, separately expression-CH=or-N=, R
1And R
2Can be identical also can be different, represent hydrogen atom, straight or branched C separately
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl, can have substituent amino or following general formula (II), wherein R
1And R
2Adjacent formation ring:
(R
3Expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl maybe can have substituent amino))
Second purpose of the present invention relates to the general formula (VIII) or (IX) preparation method of heteroaryl boron compound of expression,
(wherein, U, V, W, R
4And R
5With identical) to give a definition
It comprises: in the presence of catalyzer that contains iridium and part, make with the heteroaromatic compound of following general formula (VII) expression with following general formula (III) or (IV) the boron compound reaction of expression.
(wherein, U, V and W can be identical also can be different, separately expression-CH=or-N=, R
4And R
5Can be identical also can be different, represent hydrogen atom, straight or branched C separately
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl, can have substituent amino, or following general formula (II), wherein R
4And R
5Adjacent formation ring:
(wherein, R
3Expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl maybe can have substituent amino))
Preferred forms of the present invention
To explain the present invention in detail below.Any heteroaromatic compound can be used for the present invention's raw material heteroaromatic compound, as long as it contains a fragrant sp at least
2C h bond gets final product.
Although being used for the iridium catalyst that contains of the present invention can be catalyzer arbitrarily, as long as it is the compound that contains iridium (Ir), this contain iridium catalyst preferably below the catalyzer represented of general formula (X):
IrABn (X)
The alkene that anionicsite that the cationic moiety that it is represented by Ir, A are represented and B represent is partly formed.More preferably, the anionicsite that A represents is the chlorine atom, alkoxyl group, and hydroxyl or have or do not have substituent phenoxy group, B is compound such as the COD (1, the 5-cyclooctadiene) that contains alkene, COE (1-cyclooctene) or indenes and n are 1 or 2.Concrete example comprises IrCl (COD), IrCl (COE)
2, Ir (OMe) (COD), Ir (OH) (COD) and Ir (OPh) (COD).With respect to two (tetramethyl ethylene ketone base) two boron or tetramethyl ethylene ketone borine, its consumption is 1/100000 to 1 mole, is preferably 1/10000 to 1/10 mole.
Although the part among the present invention is not had special restriction, as long as it is and to contain iridium catalyst coordinate Lewis base, but it is preferably the bidentate Lewis base, more preferably with the compound of following general formula (XI) expression, it has the part-structure that contains or do not contain substituent dipyridyl
(wherein, R
6And R
7Can be identical also can be different, represent hydrogen atom separately, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl or contain or do not contain substituent amino, or be following general formula (II), wherein R
6And R
76 and 6 ' locates to replace in the position:
(wherein, R
3The expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl, or contain or do not contain substituent amino), the object lesson of part comprises: trialkyl phosphuret-(t)ed hydrogen, as: triphenyl phosphatization hydrogen and tributyl phosphuret-(t)ed hydrogen; Quadrol, as: Tetramethyl Ethylene Diamine and quadrol; Dipyridyl, as: 4,4 '-the di-t-butyl dipyridyl, 2,2 '-dipyridyl, 4,4 '-two-methoxyl group dipyridyl, 4,4 '-two (dimethylamino) dipyridyl, 4,4 '-dichloro dipyridyl and 4,4 '-di nitryl pyridine and 1, the 10-phenanthroline.Preferred object lesson comprises: dipyridyl, as: 4,4 '-the di-t-butyl dipyridyl, 2,2 '-dipyridyl, 4,4 '-two-methoxyl group dipyridyl, 4,4 '-two (dimethylamino) dipyridyl, 4,4 '-dichloro dipyridyl and 4,4 '-di nitryl pyridine.With respect to two (tetramethyl ethylene ketone base) diboranes or tetramethyl ethylene ketone borine, the consumption of part is 1/100000 to 1 mole, preferred 1/10000 to 1/10 mole.
Although reaction of the present invention can be carried out under solvent-free, it also is suitable being to use solvent.Do not have special restriction to being used for solvent of the present invention, as long as it does not exert an influence to reaction, the example of such solvent comprises: hydrocarbon, as: octane, pentane, heptane and hexane; Acid amides, as: dimethyl formamide and N,N-DIMETHYLACETAMIDE; Pyrrolidone, as: the N-N-methyl-2-2-pyrrolidone N-; Ketone and sulfoxide, as: acetone, ethyl methyl ketone, dimethyl sulfoxide (DMSO); Aromatic hydrocarbon, as: benzene,toluene,xylene, 1; Nitrile, as: acetonitrile; Ether, as: Di Iso Propyl Ether, tetrahydrofuran (THF) ， diox, 1,2-glycol dimethyl ether and methyl-phenoxide; Alcohol, as: methyl alcohol, ethanol, propyl alcohol, ethylene glycol and propylene glycol; Hydrocarbon as octane, pentane, heptane and hexane is preferred.Be reflected in 0 ℃～180 ℃ scopes and carry out, preferably in 10 ℃～150 ℃ scopes, carry out.
By the aforesaid aromatic heterocyclic compounds of suitable selection (I) or (VII) and aforesaid, single boronation and two boronations can be adjusted to the incidence of expectation by (III) or (IV) ratio of boron compound of expression.The incidence of single boronation and two boronations because of aromatic heterocyclic compounds (I) or (VII) and boron compound (III) or ratio (IV) change, aromatic heterocyclic compounds (I) or consumption (VI) are excessive big more, the single boronation of preferential more generation.Usually, when being purpose, with respect to boron compound (III) or (IV), use 2～100 times of moles, preferably use the aromatic heterocyclic compounds (I) of 2～50 times of moles or (VII) with single boronation.In addition, when being purpose, with respect to boron compound (III) or (IV), use 1/100 times～2 times moles, preferably use the aromatic heterocyclic compounds (I) of 1/10～1.5 times of mole or (VII) with two boronations.
Although the reaction times, temperature of reaction etc. changed to some extent because of catalytic amount,, be generally 0.2～120 hour, be preferably 2～24 hours.In addition, for preventing to cause catalyst deactivation by oxygen, reaction is preferably carried out under atmosphere of inert gases.The example of rare gas element comprises nitrogen and argon gas.In addition, although reaction pressure is not had special restriction, reaction is generally under atmospheric pressure carried out.
Although target product of the present invention can obtain by this method with the aromatic heterocycle boron compound that leads to formula V, (VI), (VIII) and (IX) represent, but, can carry out conventional purification process to improve purity, its example comprises: with the saturated brine washing, concentrate, precipitation, crystallization and distillation.In addition, the target product that obtains can be used processing such as silica gel, aluminum oxide.
Embodiment
Although hereinafter given more detailed explanation by embodiment to the present invention, the present invention only is confined to this.
Embodiment 1
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Two (tetramethyl ethylene ketone base) two boron (1mmol), heteroaromatic compound thiophene (10mmol), catalyst I rCl (COD) (0.03mmol) after part dipyridyl (dtbpy) (0.03mmol) and octane (6ml) mixes, stirs at 80 ℃ on one side and heated 16 hours.Behind the cool to room temperature, mixture with dilution with toluene, is washed with saturated brine then.After organic layer under reduced pressure concentrated, residue was removed in distillation, obtains 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene, and productive rate is 75%.
1H-NMR (400MHz, CDCl
3, TMS): δ 1.35 (s, 12H), 7.20 (dd, 1H, J=3.7 and 4.6Hz), 7.64 (d, 1H, J=4.6Hz), 7.66 (d, 1H, J=3.4Hz)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.75，84.07，128.21，132.35，137.14
MS?m/e：43(33)，110(50)，111(100)，124(82)，195(72)，210(M
+，96)
The C that calculates
10H
15BO
2The accurate molecular weight of S is: 210.0886, and actual molecular weight (found) is: 210.0881
Embodiment 2
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using pyridine (bpy) to replace dipyridyl (dtbpy), repeat the step identical with embodiment 1 as the part.Productive rate is 60%.
Embodiment 3
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using Ir (OMe) (COD) to replace IrCl (COD) to do the catalyzer, repeat the step identical with embodiment 1, descend to react 4 hours at 25 ℃.Productive rate is 88%.
Embodiment 4
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using Ir (OH) (COD) to replace IrCl (COD) to do the catalyzer, repeat the step identical with embodiment 1, descend to react 4 hours at 25 ℃.Productive rate is 86%.
Embodiment 5
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using Ir (OPh) (COD) to replace IrCl (COD) to do the catalyzer, repeat the step identical with embodiment 1, descend to react 4 hours at 25 ℃.Productive rate is 82%.
Embodiment 6
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using 1.0mmol tetramethyl ethylene ketone borine to replace two (tetramethyl ethylene ketone base) two boron, repeat the step identical with embodiment 1.Productive rate is 75%.
Embodiment 7
Synthesizing of 2-methyl-5-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using the 2-thiotolene to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 85%.
1H-NMR(400MHz，CDCl
3，TMS)：δ1.33(s，12H)，2.53(s，3H)，6.84(d，1H，J＝3.4Hz)，7.45(d，1H，J＝3.4Hz)
13C-NMR(100MHz，CDCl
3，TMS)：δ15.36，24.72，83.85，126.98，137.62，147.52
MS?m/e：123(31)，124(76)，138(85)，209(49)，224(M
+，100)
The C that calculates
11H
17BO
2The accurate molecular weight of S is: 224.1042, and actual molecular weight is: 224.1044
Embodiment 8
Synthesizing of (4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) furans:
Except using furans to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 80% (2-position boronation/3-position boronation=92/8).
1H-NMR (400MHz, CDCl
3, TMS): δ (2-isomer) 1.35 (s, 12H), 6.45 (dd, 1H, J=1.7 and 3.4Hz), 7.08 (d, 1H, J=3.4Hz), 7.66 (dd, 1H, J=1.4Hz); δ (3-isomer) 1.32 (s, 12H), 6.59 (dd, 1H, J=0.7 and 1.7Hz), 7.47 (t, 1H, J=1.5Hz), 7.78 (m, 1H)
13C-NMR (100MHz, CDCl
3, TMS): δ (2-isomer) 24.73,84.20,110.30,123.19,141.31; Do not observe the 3-isomer.
MS?m/e：43(33)，95(28)，109(31)，151(100)，179(29)，194(M
+，39)
C
10H
15BO
3Accurate molecular weight be: 194.1114, actual molecular weight is: 194.1122
Embodiment 9
2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) pyrroles's is synthetic:
Except using the pyrroles to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 60%.
1H-NMR (400MHz, CDCl
3, TMS): δ 1.32 (s, 12H), 6.30 (ddd, 1H, J=2.3,2.3 and 3.4Hz), 6.85 (ddd, 1H, J=1.2,2.2 and 3.4Hz), 7.00 (ddd, 1H, J=1.2,2.4 and 2.4Hz), 8.79 (br s, 1H)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.75，83.56，109.70，119.99，122.64
MS?m/e：107(49)，178(41)，193(M
+，100)
Embodiment 10
Synthesizing of synthetic (4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) pyridine:
Except using the 2mmol pyridine to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 60%.
1H-NMR (400MHz, CDCl
3, TMS): δ (4-isomer), (3-isomer);
13C-NMR (100MHz, CDCl
3, TMS): δ (4-isomer), (3-isomer);
MS?m/e：105(32)，106(73)，119(100)，190(99)，205(M
+，90)
C
11H
16BNO
2Accurate molecular weight be: 205.1274, actual molecular weight is: 205.1265
Embodiment 11
Synthetic 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) benzo [b] thiophene:
Except using the 4mmol thionaphthene to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 85%.
1H-NMR (400MHz, CDCl
3, TMS): δ 1.38 (s, 12H), 7.35 (ddd, 1H, J=1.7,7.3 and 8.8Hz), 7.37 (ddd, 1H, J=1.8,7.1 and 9.0Hz), 7.85 (dd, 1H, J=2.2 and 9.0Hz), 7.89 (s, 1H), 7.91 (dd, 1H, J=1.5 and 9.0Hz)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.80，84.43，122.51，124.08，124.36，125.29，134.48，140.43，143.71
MS?m/e：160(80)，174(87)，259(25)，260(M
+，100)
C
14H
17BO
2The accurate molecular weight of S is: 260.1042, and actual molecular weight is: 260.1038
Embodiment 12
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) benzo [b] furans:
Except using the 4mmol cumarone to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 87% (2-position boronation/3-position boronation=93/7).
1H-NMR (400MHz, CDCl
3, TMS): δ (2-isomer) 1.39 (s, 12H), 7.23 (t, 1H, J=7.4Hz), 7.34 (dt, 1H, J=1.2 and 7.8Hz), 7.40 (s, 1H), 7.57 (d, 1H, J=8.5Hz), 7.63 (d, 1H, J=7.8Hz), and (3-isomer) 1.37 (s, 12H), 7.26 (ddd, 1H, J=1.8,7.3 and 9.3Hz), 7.29 (ddd, 1H, J=2.1,7.3 and 9.5Hz), 7.50 (dd, 1H, J=2.4 and 6.6Hz), 7.92 (dd, 1H, J=2.7 and 9.5Hz), 7.92 (dd, 1H, J=2.4 and 6.3Hz), 7.95 (s, 1H)
13C-NMR (100MHz, CDCl
3, TMS): δ (2-isomer) 24.77,84.68,111.97,119.53,121.88,122.71,125.93,127.48,157.51; Do not observe the 3-isomer
MS?m/e：144(38)，158(25)，201(100)，244(M
+，72)
C
14H
17BO
3Accurate molecular weight be 244.1271, actual molecular weight is: 244.1274.
Embodiment 13
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) indoles:
Except using the 4mm0l indoles to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 89%.
1H-NMR(400MHz，CDCl
3，TMS)：δ1.36(s，12H)，7.09(t，1H，J＝7.7Hz)，7.11(s，1H)，7.23(t，1H，J＝8.3Hz)，7.38(d，1H，J＝8.3Hz)，7.67(d，1H，J＝7.8Hz)，8.56(br?s，1H)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.81，84.13，111.24，113.84，119.77，121.58，123.61，128.27，138.20
MS?m/e：143(35)，186(42)，242(27)，243(M
+，100)
C
14H
18BNO
2Accurate molecular weight be 243.1431, actual molecular weight is: 243.1438
Embodiment 14
Synthesizing of 3-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl)-1-(triisopropyl silyl) indoles:
Except using 4mmol N-triisopropyl silyl indoles to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 81%.
1H-NMR (400MHz, CDCl
3, TMS): δ 1.14 (d, 18H, J=7.6Hz), 1.37 (s, 12H), 1.74 (qq, 3H, J=7.6 and 7.6Hz), 7.13 (ddd, 1H, J=1.8,7.3 and 9.0Hz), 7.16 (ddd, 1H, J=1.5,7.1 and 8.5Hz), (7.50 dd, 1H, J=2.3 and 6.5Hz), 7.67 (s, 1H), 8.06 (dd, 1H, J=2.8 and 6.2Hz)
13C-NMR(100MHz，CDCl
3，TMS)：δ12.73，18.13，24.96，82.69，113.71，120.41，121.48，122.36，135.13，141.19，141.84
MS?m/e：230(28)，356(27)，399(M
+，100)
C
23H
38BNO
2The accurate molecular weight of Si is: 399.2764, and actual molecular weight is: 399.2766
Embodiment 15
Synthesizing of 1-methyl-3-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) indoles:
Except using 4mmol N-skatole to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 64%.
Embodiment 16
Synthesizing of 3-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) quinoline:
Except using quinoline to replace thiophene as the heteroaromatic compound, repeat the step identical with embodiment 1, react down at 100 ℃.Productive rate is 81%.
1H-NMR(400MHz，CDCl
3，TMS)：δ1.40(s，12H)，7.57(t，1H，J＝7.4Hz)，7.77(t，1H，J＝7.7Hz)，7.86(d，1H，J＝8.1Hz)，8.16(d，1H，J＝8.1Hz)，8.66(s，1H)，9.21(s，1H)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.93，84.35，126.48，127.58，128.42，129.37，130.54，144.28，149.45，154.81
MS?m/e：155(89)，169(54)，198(37)，240(83)，255(M
+，100)
C
15H
18BNO
2Accurate molecular weight be: 255.1430, actual molecular weight is: 255.1427.
Embodiment 17
2, the synthesizing of two (4,4,5,5-tetramethyl--1,3, the 2-dioxy boron penta ring-2-yl) thiophene of 5-:
Two (tetramethyl ethylene ketone base) two boron (1.1mmol), thiophene (1.0mmol), IrCl (COD) (0.03mmol) after dipyridyl (dtbpy) (0.03mmol) and octane (6ml) mixes, stir at 80 ℃ times on one side and heated 16 hours.Be cooled to room temperature, then with this mixture with dilution with toluene, wash with saturated brine.Organic layer under reduced pressure concentrates, and residue is removed in distillation then, obtains 0.8mmol 2, two (4,4,5,5-tetramethyl--1,3, the 2-dioxy boron penta ring-2-yl) thiophene of 5-.
1H-NMR(400MHz，CDCl
3，TMS)：δ1.34(s，24H)，7.67(s，2H)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.74，84.11，137.66
MS?m/e：43(50)，59(27)，237(43)，250(100)，321(32)，336(M
+，55)
C
16H
26B
2O
4The accurate molecular weight of S is: 336.1738, and actual molecular weight is: 336.1750
Embodiment 18
Synthesizing of two (4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) furans:
Except using furans to replace thiophene, repeat the step identical with embodiment 15 as the heteroaromatic compound.Productive rate is 70% (2,5-position two boronations/2,4-position two boronations=88/12).
1H-NMR (400MHz, CDCl
3, TMS): δ (2, the 5-isomer) 1.33 (s, 24H), 7.06 (s, 2H), (2.4-isomer) δ 1.30 (s, 24H), 7.28 (s, 1H), 7.96 (s, 1H)
13C-NMR (100MHz, CDCl
3, TMS): δ (2, the 5-isomer) 24.74,84.23,123.30, do not observe 2, the 4-isomer
MS?m/e：83(27)，235(29)，276(47)，277(100)，305(30)，320(M
+，63)
C
16H
26B
2O
5Accurate molecular weight be: 320.1966, actual molecular weight is: 320.1962
Embodiment 19
2, two (4,4,5,5-tetramethyl--1,3, the 2-dioxy boron penta ring-2-yl) pyrroles' of 5-is synthetic:
Except using the pyrroles to replace thiophene, repeat the step identical with embodiment 15 as the heteroaromatic compound.Productive rate is 79%.
1H-NMR(400MHz，CDCl
3，TMS)：δ1.31(s，24H)，6.83(d，2H，J＝2.0Hz)，9.28(br?s，1H)
13C-NMR(100MHz，CDCl
3，TMS)：δ24.73，83.71，120.35
MS?m/e：234(29)，319(M
+，100)
C
16H
27B
2NO
4Accurate molecular weight be: 319.2126, actual molecular weight is: 319.2123
Embodiment 20
Synthesizing of 2-methoxyl group-5-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using the 2-methoxythiophene to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 82%.
Embodiment 21
Synthesizing of 2-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl)-5-(trifluoromethyl) thiophene:
Except using the 2-trifluoromethyl thiophene to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 82%.
Embodiment 22
Synthesizing of 3-chloro-2-methyl-5-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl) thiophene:
Except using 3-chloro-2-thiotolene to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 79%.
Embodiment 23
3-(4,4,5,5-tetramethyl--1,3,2-dioxy boron penta ring-2-yl)-1-(triisopropyl silyl) pyrroles's is synthetic:
Except using N-triisopropyl silyl pyrroles to replace thiophene, repeat the step identical with embodiment 1 as the heteroaromatic compound.Productive rate is 77%.
1H-NMR (400MHz, CDCl
3, TMS): δ 1.09 (d, 18H, J=7.6Hz), 1.32 (s, 12H), 1.46 (qq, 3H, J=7.6Hz and 7.6Hz), 6.62 (dd, 1H, J=1.2 and 2.4Hz), 6.81 (br t, 1H, J=2.8Hz), 7.23 (br d, 1H, J=1.2Hz)
13C-NMR(100MHz，CDCl
3，TMS)：δ11.67，17.81，24.87，82.71，115.61，124.96，133.67
MS?m/e：83(35)，223(51)，224(70)，348(30)，349(M
+，100)
C
19N
36BNO
2The accurate molecular weight of Si is: 349.2608, and actual molecular weight is: 349.2605
The commercial Application ability
Preparation in accordance with the present invention is by adjusting employed aforesaid heteroaromatic chemical combination Thing (I) or (VII) and aforementioned boron compound (III) or ratio (IV) can be regulated single boronation and two boronations To the expectation ratio. The present invention be a kind of economy, simple, industrialness is good, can be with high yield Rate, simple one-step method and under temperate condition, carry out the side of list or two boronation heteroaromatic compounds Method.
Claims (11)
1. one kind with the logical formula V or (VI) preparation method of the heteroaryl boron compound of expression,
It is included under the existence of the catalyzer that contains iridium and part, make with the heteroaromatic compound of following general formula (I) expression with following general formula (III) or (IV) the boron compound reaction of expression, its formula of (V) and (VI) in X, Y, Z, R
1And R
2With identical to give a definition,
In general formula (I), X represents that Sauerstoffatom, sulphur atom maybe can have substituent imino-, Y and Z can be identical also can be different, separately expression-CH=or-N=, R
1And R
2Can be identical also can be different, represent hydrogen atom, straight or branched C separately
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl, can have substituent amino or following general formula (II), wherein R
1And R
2Adjacent formation ring:
In general formula (II), R
3Expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl maybe can have substituent amino.
2. one kind with the general formula (VIII) or (IX) preparation method of heteroaryl boron compound of expression,
It is included under the existence of the catalyzer that contains iridium and part, make with the heteroaromatic compound of following general formula (VII) expression with following general formula (III) or (IV) the boron compound reaction of expression, wherein, general formula (VIII) and (IX) in U, V, W, R
4And R
5With identical to give a definition,
In general formula (VII), U, V and W can be identical also can be different, separately expression-CH=or-N=, R
4And R
5Can be identical also can be different, represent hydrogen atom, straight or branched C separately
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl, can have substituent amino, or following general formula (II), wherein R
4And R
5Adjacent formation ring:
In general formula (II), R
3Expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl maybe can have substituent amino.
3. preparation method according to claim 1 and 2, wherein, containing iridium catalyst is the catalyzer that following general formula (X) is represented:
IrABn (X)
Wherein, A represents the chlorine atom, straight or branched C
1-8Alkoxyl group, hydroxyl or have or do not have substituent phenoxy group, B represents 1,5-cyclooctadiene or 1-cyclooctene, n represents 1 or 2.
4. preparation method according to claim 3, wherein, the A that contains in the iridium catalyst is a methoxyl group, and B is 1, and 5-cyclooctadiene, n are 1.
5. preparation method according to claim 3, wherein, the A that contains in the iridium catalyst is the chlorine atom, and B is 1, and 5-cyclooctadiene, n are 1.
6. preparation method according to claim 3, wherein, the A that contains in the iridium catalyst is the chlorine atom, and B is the 1-cyclooctene, and n is 2.
7. according to each described preparation method in the claim 1 to 6, wherein, part is the part that following general formula (XI) is represented:
Wherein, R
6And R
7Can be the same or different, represent hydrogen atom, straight or branched C separately
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl or have or do not have substituent amino, or following general formula (II), wherein R
6And R
7In the position 6 and 6 ' replace,
Wherein, R
3The expression hydrogen atom, straight or branched C
1-8Alkyl, straight or branched C
1-8Alkoxyl group, nitro, cyano group, halo C
1-8Alkyl, halogen atom, formamyl, C
1-8Acyl group, C
1-8Alkoxy carbonyl or have or do not have substituent amino.
8. preparation method according to claim 7, wherein, part is 2,2 '-dipyridyl.
9. preparation method according to claim 7, wherein, part is 4,4 '-di-t-butyl-2,2 '-dipyridyl.
10. according to each described preparation method in the claim 1 to 9, wherein, reaction is carried out in the presence of solvent.
11. preparation method according to claim 10, wherein, solvent is a hydrocarbon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61044/2002 | 2002-03-06 | ||
| JP2002061044 | 2002-03-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1639171A true CN1639171A (en) | 2005-07-13 |
| CN1318431C CN1318431C (en) | 2007-05-30 |
Family
ID=27784839
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038051877A Expired - Fee Related CN1318431C (en) | 2002-03-06 | 2003-03-05 | Process for production of heteroaryl-type boron compounds with iridium catalyst |
Country Status (5)
| Country | Link |
|---|---|
| US (3) | US7612218B2 (en) |
| EP (1) | EP1481978B1 (en) |
| JP (1) | JP4468700B2 (en) |
| CN (1) | CN1318431C (en) |
| WO (1) | WO2003074533A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011035532A1 (en) * | 2009-09-25 | 2011-03-31 | 北京大学 | Preparation method of aromatic borate ester compound |
| CN104725409A (en) * | 2015-02-09 | 2015-06-24 | 西安交通大学 | Borane-pyridine pre-ligand, preparation method and application of borane-pyridine pre-ligand, and preparation method of aryl boric acid ester |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1481978B1 (en) * | 2002-03-06 | 2011-09-14 | Mitsubishi Rayon Co., Ltd. | Process for production of heteroaryl-type boron compounds with iridium catalyst |
| US7709654B2 (en) * | 2006-09-11 | 2010-05-04 | Board Of Trustees Of Michigan State University | Process for producing oxazole, imidazole, pyrrazole boryl compounds |
| US20080091035A1 (en) * | 2006-09-11 | 2008-04-17 | Board Of Trustees Of Michigan State University | Process for the preparation of a borylated thiophene |
| US20080286812A1 (en) * | 2007-03-23 | 2008-11-20 | Joseph Thomas Ippoliti | Alcohol oxidase-based enzyme-linked immunosorbent assay |
| US7671157B2 (en) * | 2007-04-02 | 2010-03-02 | Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada, Las Vegas | Modification of polymers having aromatic groups through formation of boronic ester groups |
| WO2009111095A1 (en) | 2008-03-06 | 2009-09-11 | Dow Corning Corporation | Process for the preparation of haloalkylalkoxysilancs and haloalkylhalosilanes |
| WO2011149822A1 (en) * | 2010-05-26 | 2011-12-01 | Boehringer Ingelheim International Gmbh | 2-oxo-1,2-dihydropyridin-4-ylboronic acid derivatives |
| CN113980044B (en) * | 2021-12-03 | 2023-02-03 | 西安交通大学 | Preparation method of Ir-O-P type catalyst diboronic acid/ester compound |
| CN115536681A (en) * | 2022-09-01 | 2022-12-30 | 广西科学院 | Method for selectively synthesizing para-frequency boroester substituted anisole compound |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2285455A1 (en) * | 1997-04-09 | 1998-10-15 | Sebastian Mario Marcuccio | Process for covalently coupling organic compounds utilizing diboron derivatives |
| US6867302B2 (en) * | 2001-07-13 | 2005-03-15 | Board Of Trustees Of Michigan State University | Process for the catalytic synthesis of biaryls and polymers from aryl compounds |
| US6878830B2 (en) * | 2001-07-13 | 2005-04-12 | Board Of Trustees Of Michigan State University | Catalytic boronate ester synthesis from boron reagents and hydrocarbons |
| EP1481978B1 (en) * | 2002-03-06 | 2011-09-14 | Mitsubishi Rayon Co., Ltd. | Process for production of heteroaryl-type boron compounds with iridium catalyst |
-
2003
- 2003-03-05 EP EP03710244A patent/EP1481978B1/en not_active Expired - Lifetime
- 2003-03-05 CN CNB038051877A patent/CN1318431C/en not_active Expired - Fee Related
- 2003-03-05 WO PCT/JP2003/002569 patent/WO2003074533A1/en active Application Filing
- 2003-03-05 US US10/505,460 patent/US7612218B2/en not_active Expired - Fee Related
- 2003-03-05 JP JP2003573001A patent/JP4468700B2/en not_active Expired - Fee Related
-
2009
- 2009-09-16 US US12/560,707 patent/US8143407B2/en not_active Expired - Fee Related
-
2012
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011035532A1 (en) * | 2009-09-25 | 2011-03-31 | 北京大学 | Preparation method of aromatic borate ester compound |
| CN102030770B (en) * | 2009-09-25 | 2012-10-31 | 北京大学 | Preparation method of aromatic boronic acid ester composite |
| CN104725409A (en) * | 2015-02-09 | 2015-06-24 | 西安交通大学 | Borane-pyridine pre-ligand, preparation method and application of borane-pyridine pre-ligand, and preparation method of aryl boric acid ester |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2003074533A1 (en) | 2003-09-12 |
| US7612218B2 (en) | 2009-11-03 |
| EP1481978A4 (en) | 2008-02-20 |
| JP4468700B2 (en) | 2010-05-26 |
| US8143407B2 (en) | 2012-03-27 |
| US20100010224A1 (en) | 2010-01-14 |
| US20120142924A1 (en) | 2012-06-07 |
| JPWO2003074533A1 (en) | 2005-06-30 |
| CN1318431C (en) | 2007-05-30 |
| US20050148775A1 (en) | 2005-07-07 |
| EP1481978B1 (en) | 2011-09-14 |
| EP1481978A1 (en) | 2004-12-01 |
| US8507680B2 (en) | 2013-08-13 |
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